This invention relates to the technical field of fiber-reactive azo dyes.
Dyes conforming to the hereinbelow indicated general formulae 1 and 2 are known from EP-A 94055, EP-A 144766 and EP-A 775732. However, these dyes have certain application defects, for example an excessive dependence of the color yield on changing dyeing parameters in the dyeing process, or an insufficient or unlevel color build-up on cotton (good color build-up follows from the ability of a dye to produce a correspondingly stronger dyeing from an increased dye concentration in the dyebath). Possible consequences of these shortcomings are poor reproducibilities for the dyeings which are obtainable.
However, it is particularly important to obtain dyeings having a good color yield, i.e., dyeings whose depth of shade is very high in relation to the amount of dye used, for example in comparison with other dyes, because of the coloring property of the dye itself (high absorbance) and because of the dyeing characteristics of this dye, such as good affinity and high yield of fixation. If mixtures of dyes having a certain color yield are used, the color yield of this mixture of dyes will generally be the average of the color yields of the individual dyes, which is why the color yield of a mixture of, for example, two dyes will be less than the color yield obtained when the dye having the larger color yield property is used as the only dye but in the total amount of the two individual dyes.
It has now been found that the color strength of the hereinbelow described dye mixtures according to the invention is surprisingly higher than the sum total of the color strengths afforded by the individual dyes in the mixture. This synergistic effect also shows itself in improved build-up characteristics on the part of the mixture of the invention compared with the individual dyes in the mixture.
It is true that synergistic mixtures of certain reactor dyes are already known from EP-A 681002, but the mixtures described therein have certain application defects, for example an unlevel build-up in the cold pad-batch process, and also the staining of adjacent fabric, especially polyester, in continuous dyeing by the pad-steam process. This staining is undesirable because it means that, in commercial practice, the dyed material has to be subjected to several energy- and media-intensive (water) cleaning operations to remove the stains. The present invention also provides a way of reducing this staining while improving the build-up characteristics of the mixture according to the invention compared with the individual dyes in the mixture.
The present invention accordingly provides dye mixtures comprising one or more azo dyes of the general formula (1) and one or more azo dyes of the general formula (2) 
where
M is an alkali metal, an ammonium or the equivalent of an alkaline earth metal;
X, X1 and X2 are independently fluoro, chloro, alkoxy, hydroxyl, cyanamido, amino, anilino, sulfoanilino or alkylamino;
Y, Y1 and Y2 are independently ethenyl or a grouping of the formula xe2x80x94CH2CH2Z, where
Z is an alkali-eliminable grouping;
R1, R2, R3, R4, R5 and R6 are independently hydrogen, alkyl, alkoxy, sulfo, hydroxyl, cyano, chloro or bromo;
B is an alkylenediamino bridge of the general formula D or E or F 
where n, m and o are independently from 1 to 4;
A and G combine with the joining nitrogen atom to form a morpholine or piperazine radical; or
A is hydrogen, (C1-C4)-alkyl, which may be substituted, phenyl or phenyl substituted by alkyl, alkoxy, sulfo, hydroxyl, cyano, chloro or bromo; and
G has one of the meanings of A or is a fiber-reactive radical of the general formula H, I or J 
t where p, q and r are independently from 1 to 4;
Y3, Y4 and Y5 independently have one of the meanings of Y1; and
R7 and R8 are independently hydrogen, alkyl, alkoxy, sulfo, hydroxyl, cyano, chloro or bromo.
Alkyl R and any alkyl substituent on phenyl A may be straight-chain or branched and be for example methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, pentyl or hexyl. Preference is given to (C1-C4)-alkyl groups, and methyl and ethyl are particularly preferred. Similarly, (C1-C4)-alkyl A is preferably methyl or ethyl.
The same logic rules for alkoxy groups, which are thus preferably (C1-C4)-alkoxy groups and particularly preferably methoxy and ethoxy, and also for alkylamine X. The latter is preferably (C1-C4)-alkylamine and particularly preferably methylamine or ethylamine.
Alkyl metal M is preferably sodium, potassium or lithium, particularly preferably sodium. The equivalent of an alkaline earth metal M is preferably the equivalent of calcium.
An alkali-eliminable grouping Z is, for example, chloro, acetyl, phosphato or preferably sulfato.
M is preferably sodium, i.e., the dyes in dye mixtures according to the invention are preferably in the form of their sodium salts. The X radicals are each preferably independently chloro or fluoro, and the Y radicals are each preferably ethenyl or xcex2-sulfatoethyl. The groups xe2x80x94SO2Y, xe2x80x94SO2Y1 and xe2x80x94SO2Y2 are preferably disposed para relative to the diazo group. The xe2x80x94SO2Y5 group is preferably disposed para or meta relative to the amino group. R1 to R8 are each preferably independently hydroxyl, methyl, methoxy, sulfo and particularly preferably hydrogen. Most preferably R1 to R8 are all hydrogen. n, m, p, q and r are each preferably 2 or 3. B is for example 1,3- to 1,6-(C3-C6)-alkylenediamino, 1,5-diamino-3-oxapentane, and is particularly preferably N-(2-hydroxyethyl)-ethylenediamino. A is preferably hydrogen, methyl or phenyl, while G is preferably 3-sulfophenyl, 3-(xcex2-sulfatoethylsulfonyl)-phenyl or 3-(xcex2-sulfatoethylsulfonyl)-propyl. Particularly preferably G is 2-(xcex2-sulfatoethylsulfonyl)-ethyl or 4-(xcex2-sulfatoethylsulfonyl)-phenyl.
In particularly preferred dye mixtures according to the invention, R1 to R8 are each hydrogen, the groups xe2x80x94SO2Y, xe2x80x94SO2Y1 and xe2x80x94SO2Y2 are disposed para relative to the diazo group and Y, Y1 and Y2 are each ethenyl or xcex2-sulfatoethyl, A is hydrogen, methyl or phenyl, X, X1 and X2 are each fluoro or chloro, and G is 2-(xcex2-sulfatoethyl-sulfonyl)-ethyl, 4-(xcex2-sulfatoethylsulfonyl)-phenyl or is a radical of the general formula I with q=r=2.
In general, the azo dye of the general formula (1) and the azo dye of the general formula (2) are present in the dye mixture of the invention in a blend ratio of 90:10% by weight to 10:90% by weight, preferably in a ratio of 70:30% by weight to 30:70% by weight. Particularly preferably they are present in the mixture in a ratio of 65:35 to 35:65% by weight.
The dye mixtures of the invention can be present as a preparation in solid or in liquid (dissolved) form. In solid form, they generally include the electrolyte salts customary for water-soluble and especially for fiber-reactive dyes, such as sodium chloride, potassium chloride and sodium sulfate, and may further include the auxiliaries customary in commercial dyes, such as buffer substances capable of setting a pH in aqueous solution between 3 and 7, such as sodium acetate, sodium borate, sodium bicarbonate, sodium dihydrogenphosphate, sodium tricitrate and disodium hydrogen phosphate, or small amounts of siccatives; if they are present in a liquid, aqueous solution (including the presence of thickeners of the type customary in print pastes), they may also include substances which ensure a long life for these preparations, for example mold preventatives.
In general, the dye mixtures of the invention are present as dye powders containing 10 to 80% by weight, based on the dye powder or the preparation, of an electrolyte salt which is also referred to as a standardizing agent. These dye powders may additionally include the aforementioned buffer substances in a total amount of up to 10% by weight, based on the dye powder. If the dye mixtures of the invention are present in aqueous solution, the total dye content of these aqueous solutions will be up to about 50% by weight, for example between 5 and 50% by weight, and the electrolyte salt content of these aqueous solutions will preferably be below 10% by weight, based on the aqueous solution; the aqueous solutions (liquid preparations) may include the aforementioned buffer substances in an amount which is generally up to 10% by weight, for example 0.1 to 10% by weight, preference being given to 2% by weight, especially 0.1 to 2% by weight.
The present invention also relates to the preparation of dye mixtures according to the invention. This may be effected in a conventional manner, by mechanically mixing the solid or liquid individual dyes of the general formulae 1 and 2 in the desired blend ratio. The requisite individual dyes of the general formulae 1 and 2 are known and can be prepared according to processes known per se, or else acquired commercially.
However, the dye mixtures according to the invention may also be obtained by direct synthesis. This may be effected by, in a conventional manner, reacting 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid with cyanuric chloride or cyanuric fluoride, then
with a mixture of one or more amines of the general formula Da, Ea or Fa 
where n, m and o are each as defined above, and one or more amines of the general formula Ha, Ia or Ja 
where p, r, A, Y3, Y4, Y5, R7 and R8 are each as defined above,
b) subsequently with a mixture of diazonium salts of the amines of the general formulae (3), (4) and (5) 
where R1, R2, R3, R4, R5, R6, Y, Y1 and Y2 are each as defined, or
performing the steps a) and b) in the reverse order, and subsequently, if X, X1 and X2 are not chloro or fluoro, reacting the resulting products with a compound of the general formula R9OH, where R9 is hydrogen or alkyl, or with an amine of the general formula R10NH2, where R10 is hydrogen, cyano, alkyl, phenyl or sulfophenyl.
In a preferred embodiment of the preparation process according to the invention, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid is reacted with cyanuric chloride or cyanuric fluoride in a conventional manner, for example at a temperature between 0 and 40xc2x0 C., preferably between 0 and 20xc2x0 C., and at a pH between 0 and 8, preferably between 1 and 5, and the resulting reaction mixture is admixed with a mixture of an amino compound of the general formula Da, Ea or Fa and an amino compound of the general formula Ha, Ia or Ja and reacted therewith in a conventional manner, for example at a temperature between 0 and 60xc2x0 C., preferably between 10 and 40xc2x0 C., and at a pH between 1 and 8, preferably between 3 and 5.
The resulting diaminohalotriazine compounds are then finally reacted with a diazonium salt prepared from an amine of the general formula (3) in a well known manner to form a dye mixture according to the invention in a conventional manner, for example at a temperature between 10 and 50xc2x0 C., preferably between 20 and 35xc2x0 C., and at a pH between 3 and 7, preferably between 4 and 5.
The reaction of dyes of the general formulae 1 and 2 where the X radicals are each fluoro or chloro with alcohols of the general formula R9OH or amines of the general formula R10NH2 may be carried out in a conventional manner, for example at a temperature between 10 and 100xc2x0 C., preferably between 40 and 80xc2x0 C., and at a pH between 3 and 7, preferably between 4 and 5.
The separation from their synthesis solution of the chemically prepared dye mixtures of the invention can be effected according to generally known methods, for example either by precipitating from the reaction medium by means of electrolytes, for example sodium chloride or potassium chloride, or by evaporating or spray-drying the reaction solution, in which case this reaction solution may have a buffer substance added to it.
The dye mixtures of the invention have useful application properties. They are used for dyeing or printing hydroxyl- and/or carboxamido-containing materials, for example in the form of sheetlike structures, such as paper and leather or of films, for example composed of polyamide, or in bulk, as for example of polyamide and polyurethane, but especially for dyeing or printing these materials in fiber form. Similarly, the as-synthesized solutions of the dye mixtures of the invention, if appropriate after addition of a buffer substance and if appropriate after concentrating or diluting, can be used directly as liquid preparation for dyeing.
The present invention thus also relates to the use of the dye mixtures of the invention for dyeing or printing these materials, or rather to processes for dyeing or printing these materials in a conventional manner, by using a dye mixture of the invention as colorant. The materials are preferably employed in the form of fiber materials, especially in the form of textile fibers, such as woven fabrics or yarns, as in the form of hanks or wound packages.
Hydroxyl-containing materials are those of natural or synthetic origin, for example cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers, such as linen, hemp, jute and ramie fibers; regenerated cellulose fibers are for example staple viscose and filament viscose.
Carboxamido-containing materials are for example synthetic and natural polyamides and polyurethanes, especially in the form of fibers, for example wool and other animal hairs, silk, leather, nylon-6,6, nylon-6, nylon-11 and nylon-4.
The dye mixtures of the invention can be applied to and fixed on the substrates mentioned, especially the fiber materials mentioned, by the application techniques known for water-soluble dyes, especially fiber-reactive dyes.
For instance, on cellulose fibers they produce by the exhaust method from a long liquor using various acid-binding agents and optionally neutral salts, such as sodium chloride or sodium sulfate, dyeings having very good color yields which are improved compared with the individual dyes of the general formulae 1 and 2. Application is preferably from an aqueous bath at temperatures between 40 and 105xc2x0 C., optionally at a temperature of up to 130xc2x0 C. under superatmospheric pressure, and optionally in the presence of customary dyeing auxiliaries. One possible procedure is to introduce the material into the warm bath and to gradually heat the bath to the desired dyeing temperature and to complete the dyeing process at that temperature. The neutral salts which accelerate the exhaustion of the dyes may also, if desired, only be added to the bath after the actual dyeing temperature has been reached.
The padding process likewise provides excellent color yields and very good color build-up on cellulose fibers, the dyes being allowed to become fixed on the material by batching at room temperature or at elevated temperature, for example at up to 60xc2x0 C., by steaming or using dry heat in a conventional manner.
Similarly, the customary printing processes for cellulose fibers, which can be carried out either single-phase, for example by printing with a print paste comprising sodium bicarbonate or some other acid-binding agent and by subsequent steaming at 100 to 103xc2x0 C., or two-phase, for example by printing with a neutral or weakly acidic print colour and subsequent fixation either by passing the printed material through a hot electrolyte-comprising alkaline bath or by overpadding with an alkaline electrolyte-comprising padding liquor with subsequent batching of the alkali-overpadded material or subsequent steaming or subsequent treatment with dry heat, produce strong prints with well-defined contours and a clear white ground. The appearance of the prints is not greatly affected by variations in the fixing conditions.
When fixing by means of dry heat in accordance with the customary thermofix processes, hot air from 1 20 to 200xc2x0 C. is used. In addition to the customary steam at 101 to 103xc2x0 C. it is also possible to use superheated steam and high-pressure steam at temperatures of up to 160xc2x0 C.
The acid-binding agents which effect the fixation of the dyes of the dye mixtures of the invention on the cellulose fibers include for example water-soluble basic salts of the alkali metals and likewise alkaline earth metals of inorganic or organic acids or compounds which liberate alkali in the heat. Especially suitable are the alkali metal hydroxides and alkali metal salts of weak to medium inorganic or organic acids, the preferred alkali metal compounds being the sodium and potassium compounds. Such acid-binding agents include for example sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium-formate, sodium-dihydrogenphosphate, disodium hydrogenphosphate, sodium trichloroacetate, waterglass or trisodium phosphate.
The dye mixtures of the invention are notable for a high yield of fixation when applied to the cellulose fiber materials by dyeing or printing. The cellulose dyeings obtained following the customary aftertreatment by rinsing to remove unfixed dye portions exhibit excellent wetfastnesses, in particular since such unfixed dye portions are easily washed off on account of their good solubility in cold water.
The dyeings and prints obtainable with the dye mixtures of the invention have bright hues; especially the dyeings and prints on cellulose fiber materials have good lightfastness and very good wetfastnesses, such as wash, milling, water, seawater, crossdyeing and acidic and also alkaline perspiration fastness properties, also good fastness to pleating, hotpressing and rubbing.
Furthermore, the dye mixtures of the invention can also be used for the fiber-reactive dyeing of wool. Moreover, wool which has been given a nonfelting or low-felting finish (cf. for example H. Rath, Lehrbuch der Textilchemie, Springer-Verlag, 3rd Edition (1972), p. 295-299, especially the finish by the Hercosett process (p. 298); J. Soc. Dyers and Colourists 1972, 93-99, and 1975, 33-44) can be dyed with very good fastness properties.
The process of dyeing on wool is here carried out in a conventional manner from an acidic medium. For instance, acetic acid and/or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. To obtain a dyeing of acceptable levelness, it is advisable to add a customary leveling agent, for example on the basis of a reaction product of cyanuric chloride with 3 times the molar amount of an aminobenzenesulfonic acid and/or of an aminonaphthalenesulfonic acid or on the basis of a reaction product of for example stearylamine with ethylene oxide. For instance, the dye mixture of the invention is preferably subjected to the exhaust process initially from an acidic dyebath having a pH of about 3.5 to 5.5 under pH control and the pH is then, toward the end of the dyeing time, shifted into the neutral and optionally weakly alkaline range up to a pH of 8.5 to bring about, especially for very deep dyeings, the full reactive bond between the dyes of the dye mixtures of the invention and the fiber. At the same time, the dye portion not reactively bound is removed.
The procedure described herein also applies to the production of dyeings on fiber materials composed of other natural polyamides or of synthetic polyamides and polyurethanes. In general, the material to be dyed is introduced into the bath at a temperature of about 40xc2x0 C., agitated therein for some time, the dyebath is then adjusted to the desired weakly acidic, preferably weakly acetic acid, pH and the actual dyeing is carried out at a temperature between 60 and 98xc2x0 C. However, the dyeings can also be carried out at the boil or in sealed dyeing apparatus at temperatures of up to 106xc2x0 C. Since the water solubility of the dye mixtures of the invention is very good, they can also be used with advantage in customary continuous dyeing processes. The color strength of the dye mixtures of the invention is very high.
The dye mixtures of the invention dye the materials mentioned, preferably fiber materials, in bright red to bluish red shades.